CN108083264A - A kind of preparation method of three-dimensional grapheme - Google Patents
A kind of preparation method of three-dimensional grapheme Download PDFInfo
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- CN108083264A CN108083264A CN201810158507.8A CN201810158507A CN108083264A CN 108083264 A CN108083264 A CN 108083264A CN 201810158507 A CN201810158507 A CN 201810158507A CN 108083264 A CN108083264 A CN 108083264A
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- dimensional grapheme
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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Abstract
The present invention provides a kind of preparation method of three-dimensional grapheme, first using centrifugal mixer graphene oxide particle is made to be scattered in absolute ethyl alcohol, graphene oxide and absolute ethyl alcohol are made using stirring technique afterwards, reduction substrate liquid uniformly disperses, then graphene oxide is made to be transformed into three-dimensional grapheme and obtains three-dimensional grapheme gel using hydro-thermal reaction, three-dimensional grapheme powder is obtained finally by vacuum freeze-drying method, the three-dimensional grapheme powder being prepared using method provided by the invention, its is simple for process, it is easy to operate, it is efficient, whole preparation process is safety contamination-free residual again, the three-dimensional grapheme powder purity being prepared is high, its purity is up to more than 99.80%.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of preparation method of three-dimensional grapheme.
Background technology
Graphene has an outstanding electrical and optical properties, huge specific surface area and excellent mechanical performance make its
The fields such as field-effect transistor, transparent conductive film, energy storage material have broad application prospects, and are with honeycomb crystal lattice knot
The plane 2D stratified materials of structure, three-dimensional grapheme are graphite alkylenes in recent years then by the assembly that forms of 2D graphene films integration
The new type functional material in field, 2D graphene films are integrated into the assembly with 3D structures can be with Effective Regulation graphene
Electricity, optics, machinery, chemistry and catalysis characteristics, 3D grapheme materials not only have the intrinsic physicochemical property of graphene, thirdly
Tie up porous micro/nano structure also have both it large specific surface area, high mechanical strength, electronic conduction ability are superior and mass transfer is quick
Good characteristics are waited, has in the fields such as catalysis, hydrogen storage/gas absorption, sensor, environment remediation, ultracapacitor and greatly should very much
With value.
The content of the invention
The more than prior art is based on, it is an object of the invention to provide a kind of preparation method of three-dimensional grapheme, using this
The 3D graphenes that the method that invention provides is prepared, have.
In order to achieve the goal above, the technical solution adopted by the present invention is：A kind of preparation method of three-dimensional grapheme, including
Following steps：
Step 1, by weight ratio be 1：0.8~1.5 graphene oxide carries out centrifugal mixer 3~5 minutes with absolute ethyl alcohol,
It is followed by stirring for 30 minutes or more, reduction substrate liquid is added in the rate of 3~10g/min during stirring, is mixed after stirring
Suspension is closed, wherein, the weight ratio of graphene oxide and reduction substrate liquid is 1~3 in mixing suspension：3~5；
Wherein, the raw material of the reduction substrate liquid includes the component of following parts by weight：40~55 parts of substrate liquid, 12~15
The reducing agent of part, the substrate liquid are 10~20 by weight ratio：5~15：5~10 water, ethyl alcohol, polyethylene glycol are mixed to prepare；
Step 2, the mixing suspension for obtaining step 1 are placed in thermal response kettle, and water is carried out under the conditions of 175~210 DEG C
The three-dimensional grapheme gel derived above when small of thermal response 10；
The three-dimensional grapheme gel progress vacuum freeze drying that step 2 obtains is obtained three-dimensional grapheme powder by step 3
End.
The method provided by the invention for preparing three-dimensional grapheme, is first scattered in graphene oxide particle using centrifugal mixer
In absolute ethyl alcohol, also make to disperse between graphene oxide particle, centrifugal mixer can only disperse graphene oxide, but be not achieved
Even scattered effect, therefore then carried out graphene oxide and absolute ethyl alcohol and reduction substrate liquid uniformly using stirring technique
Stirring, reduction substrate liquid includes substrate liquid and reducing agent, and substrate liquid is mixed to prepare using water, ethyl alcohol, polyethylene glycol, and ethyl alcohol makes
Reduction substrate liquid be more easy to mix with graphene oxide, polyethylene glycol make graphene in mixing suspension more uniformly disperse and
Do not settle, also make it is scattered after graphene particles not cluster, in hydro-thermal reaction, graphene oxide particle is in reducing agent and high temperature
Under the conditions of reduction obtain three-dimensional grapheme, and the substantially all evaporation of ethyl alcohol in mixing suspension, water and polyethylene glycol then part
Evaporation forms three-dimensional grapheme gel, water, poly- second two during vacuum freeze drying afterwards in gel after flow of water reaction
Alcohol, which freezes, to be distilled and takes away remaining reducing agent in gel.
As an optimization, the particle size of graphene oxide is less than 300 nanometers in the step 1, using graphene oxide
Particle it is smaller, purity is higher, and the properties of final obtained three-dimensional grapheme are higher.
As an optimization, the rate of centrifugal mixer is carried out in the step 1 as 800~950r/min, centrifugation rate is too low, oxygen
Graphite alkene particle is not easy to disperse in absolute ethyl alcohol, and centrifugation rate is excessively high, and graphene oxide dispersion degree in absolute ethyl alcohol is equal
Evenness is too low, and stirring technique afterwards is not easy to be allowed to homodisperse.
As another optimization, the purpose that centrifugal mixer is carried out in the step 1 is that graphene oxide particle is made to be scattered in nothing
In water-ethanol, and in centrifugal mixer, centrifugal force effect graphene oxide particle is made to be scattered in absolute ethyl alcohol, and because everywhere from
The difference of mental and physical efforts, graphene particles cannot be dispersed in absolute ethyl alcohol, therefore then using stirring technique, the process of stirring
In reduction substrate liquid is added in batches, reduction substrate liquid is made uniformly to be mixed with graphene oxide and absolute ethyl alcohol, so as to obtain
To the mixing suspension of good dispersion, as an optimization, the rate of stirring is using 350~500r/min, excessively slow stirring unevenness
It is even, it is too fast easy to foaming.
As an optimization, the raw material of substrate liquid is reduced in the step 1 includes the component of following parts by weight：48 parts of substrate
Liquid, 14 parts of reducing agent, the substrate liquid are 15 by weight ratio：9：7 water, ethyl alcohol, polyethylene glycol are mixed to prepare
As further optimization, reducing agent is oxalic acid in the step 1, hydrogen chloride, concentration are 85~90% ammonium hydroxide, L-
Cysteine, reducing agent is preferred water-soluble or ethyl alcohol dissolubility, so during vacuum freeze drying, reducing agent be more easy to
Water distils with ethyl alcohol, so that the purity of the three-dimensional grapheme powder arrived is high.
As further optimization, the reducing agent is that weight ratio is 1~3：1~3：5~8 L-cysteine, chlorination
Hydrogen is the mixture of 85~90% ammonium hydroxide with concentration
As an optimization, the technique being freeze-dried in the step 3 is specially：Subzero 35~45 DEG C are first cooled to obtain
Gel freezing material, is then evacuated to 1~5Pa, is then cooled to subzero 55~65 DEG C, treats that the ice in gel freezing material all rises
Three-dimensional grapheme powder is obtained after China.
Description of the drawings
Fig. 1 to 3 is electron-microscope scanning picture of the obtained three-dimensional grapheme of the invention under different amplification.
Advantageous effect
Beneficial effects of the present invention are as follows：
(1), the preparation method of three-dimensional grapheme provided by the invention first makes graphene oxide particle point using centrifugal mixer
It dissipates in absolute ethyl alcohol, using stirring technique graphene oxide is made to be uniformly dispersed with absolute ethyl alcohol, reduction substrate liquid afterwards, then
Using hydro-thermal reaction graphene oxide is made to be transformed into three-dimensional grapheme and obtain three-dimensional grapheme gel, it is cold finally by vacuum
Freeze seasoning and obtain three-dimensional grapheme powder.
(2), the three-dimensional grapheme powder being prepared using method provided by the invention, it is simple for process, it is easy to operate,
Efficient, whole preparation process is safety contamination-free residual again, and the three-dimensional grapheme powder purity being prepared is high, purity
Up to more than 99.80%.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
The present embodiment provides a kind of preparation methods of three-dimensional grapheme, comprise the following steps：
Step 1, by weight ratio be 1：0.8 particle size be less than 300 nanometers of graphene oxide and absolute ethyl alcohol with
The rate of 800r/min carries out centrifugal mixer 3 minutes, is then stirred 60 minutes with the rate of 350r/min, with 4g/ during stirring
The rate of min adds in reduction substrate liquid, and mixing suspension is obtained after stirring, wherein, graphene oxide in mixing suspension
Weight ratio with reducing substrate liquid is 1：3；
Wherein, the raw material of the reduction substrate liquid includes the component of following parts by weight：40 parts of substrate liquid, 12 parts of reduction
Agent, the substrate liquid are 10 by weight ratio：5：5 water, ethyl alcohol, polyethylene glycol are mixed to prepare, and the reducing agent is hydrogen chloride；
Step 2, the mixing suspension for obtaining step 1 are placed in thermal response kettle, and hydro-thermal reaction is carried out under the conditions of 175 DEG C
15 obtain three-dimensional grapheme gel when small；
Step 3, the three-dimensional grapheme gel for obtaining step 2 carry out vacuum freeze drying, and technique is specially：First cool down
Gel freezing material is obtained to subzero 35 DEG C, 4~5Pa is then evacuated to, is then cooled to subzero 55 DEG C, is treated in gel freezing material
Ice all distillation after i.e. obtain three-dimensional grapheme powder.
Embodiment 2
The present embodiment provides a kind of preparation methods of three-dimensional grapheme, comprise the following steps：
Step 1, by weight ratio be 1：1.2 particle size be less than 300 nanometers of graphene oxide and absolute ethyl alcohol with
The rate of 890r/min carries out centrifugal mixer 4 minutes, is then stirred 60 minutes with the rate of 420r/min, with 6g/ during stirring
The rate of min adds in reduction substrate liquid, and mixing suspension is obtained after stirring, wherein, graphene oxide in mixing suspension
Weight ratio with reducing substrate liquid is 2.5：4；
Wherein, the raw material of the reduction substrate liquid includes the component of following parts by weight：48 parts of substrate liquid, 14 parts of reduction
Agent, the substrate liquid are 15 by weight ratio：11：7 water, ethyl alcohol, polyethylene glycol are mixed to prepare, and the reducing agent is that weight ratio is
2：2：7 L-cysteine, hydrogen chloride and concentration is the mixture of 88% ammonium hydroxide；
Step 2, the mixing suspension for obtaining step 1 are placed in thermal response kettle, and hydro-thermal reaction is carried out under the conditions of 200 DEG C
20 obtain three-dimensional grapheme gel when small；
Step 3, the three-dimensional grapheme gel for obtaining step 2 carry out vacuum freeze drying, and technique is specially：First cool down
Gel freezing material is obtained to subzero 42 DEG C, 1~3Pa is then evacuated to, is then cooled to subzero 60 DEG C, is treated in gel freezing material
Ice all distillation after i.e. obtain three-dimensional grapheme powder.
Embodiment 3
The present embodiment provides a kind of preparation methods of three-dimensional grapheme, comprise the following steps：
Step 1, by weight ratio be 1：1.5 particle size be less than 300 nanometers of graphene oxide and absolute ethyl alcohol with
The rate of 950r/min carries out centrifugal mixer 3 minutes, is then stirred 50 minutes with the rate of 500r/min, with 10g/ during stirring
The rate of min adds in reduction substrate liquid, and mixing suspension is obtained after stirring, wherein, graphene oxide in mixing suspension
Weight ratio with reducing substrate liquid is 3：5；
Wherein, the raw material of the reduction substrate liquid includes the component of following parts by weight：55 parts of substrate liquid, 15 parts of reduction
Agent, the substrate liquid are 20 by weight ratio：15：10 water, ethyl alcohol, polyethylene glycol are mixed to prepare, and the reducing agent is weight ratio
For 3：3：8 L-cysteine, hydrogen chloride and concentration is the mixture of 90% ammonium hydroxide；
Step 2, the mixing suspension for obtaining step 1 are placed in thermal response kettle, and hydro-thermal reaction is carried out under the conditions of 210 DEG C
10 obtain three-dimensional grapheme gel when small；
Step 3, the three-dimensional grapheme gel for obtaining step 2 carry out vacuum freeze drying, and technique is specially：First cool down
Gel freezing material is obtained to subzero 45 DEG C, 2~4Pa is then evacuated to, is then cooled to subzero 62 DEG C, is treated in gel freezing material
Ice all distillation after i.e. obtain three-dimensional grapheme powder.
The three-dimensional grapheme powder obtained in above-described embodiment 1 to 3, purity respectively reaches 99.82%, 99.99%,
More than 99.85%, available in the fields such as reinforcement, catalysis, hydrogen storage/gas absorption, sensor, environment remediation, ultracapacitor,
Wherein, it is most preferred embodiment with the purity highest of the three-dimensional grapheme obtained in embodiment 2.
Carry out the embodiment that the present invention will be described in detail above by embodiment, whereby to the present invention how application technology means
Technical problem is solved, and the realization process for reaching technique effect can fully understand and implement according to this.It should be clear that as long as
Conflict is not formed, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and be formed
Technical solution is within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of three-dimensional grapheme, which is characterized in that comprise the following steps：
Step 1, by weight ratio be 1：0.8~1.5 graphene oxide carries out centrifugal mixer 3~5 minutes with absolute ethyl alcohol, then
Stirring 30 minutes or more adds in reduction substrate liquid with the rate of 3~10g/min during stirring, it is outstanding that mixing is obtained after stirring
Turbid, wherein, the weight ratio of graphene oxide and reduction substrate liquid is 1~3 in mixing suspension：3~5；
Wherein, the raw material of the reduction substrate liquid includes the component of following parts by weight：40~55 parts of substrate liquid, 12~15 parts
Reducing agent, the substrate liquid are 10~20 by weight ratio：5~15：5~10 water, ethyl alcohol, polyethylene glycol are mixed to prepare；
Step 2, the mixing suspension for obtaining step 1 are placed in thermal response kettle, and it is anti-that hydro-thermal is carried out under the conditions of 175~210 DEG C
Answer 10 it is small when three-dimensional grapheme gel derived above；
The three-dimensional grapheme gel progress vacuum freeze drying that step 2 obtains is obtained three-dimensional grapheme powder by step 3.
2. the preparation method of three-dimensional grapheme according to claim 1, which is characterized in that graphene oxide in the step 1
Particle size be less than 300 nanometers.
3. the preparation method of three-dimensional grapheme according to claim 1, which is characterized in that centrifugation is carried out in the step 1 and is stirred
The rate mixed is 800~950r/min.
4. the preparation method of three-dimensional grapheme according to claim 1, which is characterized in that be stirred in the step 1
Rate be 350~500r/min.
5. the preparation method of three-dimensional grapheme according to any one of claims 1 to 4, which is characterized in that in the step 1 also
The raw material of former base bottom liquid includes the component of following parts by weight：48 parts of substrate liquid, 14 parts of reducing agent, the substrate liquid is by weight
Than for 15：9：7 water, ethyl alcohol, polyethylene glycol are mixed to prepare.
6. the preparation method of three-dimensional grapheme according to any one of claims 1 to 4, which is characterized in that in the step 1 also
Former agent is oxalic acid, hydrogen chloride, concentration are 85~90% ammonium hydroxide, L-cysteine.
7. the preparation method of three-dimensional grapheme according to claim 6, which is characterized in that reducing agent is in the step 1
Weight ratio is 1~3：1~3：5~8 L-cysteine, hydrogen chloride and concentration is the mixture of 85~90% ammonium hydroxide.
8. the preparation method of three-dimensional grapheme according to any one of claims 1 to 4, which is characterized in that in the step 3 into
Row freeze-drying technique be specially：It is first cooled to subzero 35~45 DEG C and obtains gel freezing material, be then evacuated to 1~5Pa,
Then subzero 55~65 DEG C are cooled to, three-dimensional grapheme powder is obtained after the ice in gel freezing material all distillation.
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Cited By (3)
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| CN108529603A (en) * | 2018-06-26 | 2018-09-14 | 西南交通大学 | Alcohol heat-treats the method and graphene of graphene oxide |
| CN111847376A (en) * | 2020-07-02 | 2020-10-30 | 上海集成电路研发中心有限公司 | Humidity sensor manufacturing method |
| CN113593917A (en) * | 2021-07-23 | 2021-11-02 | 阜阳师范大学 | Synthesis method of cellular three-dimensional graphene and application of cellular three-dimensional graphene in quasi-solid-state dye-sensitized solar cell |
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Application publication date: 20180529 |